Coating compositions for use with an overcoated photoresist

ABSTRACT

Coating compositions for use with an overcoated photoresist are provided where the coating composition comprises a resin containing cyanurate groups and hydrophobic groups. The coating composition can enhance resolution of an overcoated photoresist relief image.

This application claims the benefit of priority under 35 U.S.C. §119(e)to U.S. Provisional Application No. 61/216,794, filed May 20, 2009, thecontents of which application are incorporated herein by reference.

The present invention relates to cyanurate resins that are particularlyuseful as a component of a coating composition underlying an overcoatedphotoresist.

Photoresists are photosensitive films used for the transfer of images toa substrate. A coating layer of a photoresist is formed on a substrateand the photoresist layer is then exposed through a photomask to asource of activating radiation. The photomask has areas that are opaqueto activating radiation and other areas that are transparent toactivating radiation. Exposure to activating radiation provides aphotoinduced or chemical transformation of the photoresist coating tothereby transfer the pattern of the photomask to the photoresist-coatedsubstrate. Following exposure, the photoresist is developed to provide arelief image that permits selective processing of a substrate.

A major use of photoresists is in semiconductor manufacture where anobject is to convert a highly polished semiconductor slice, such assilicon or gallium arsenide, into a complex matrix of electronconducting paths that perform circuit functions. Proper photoresistprocessing is a key to attaining this object. While there is a stronginterdependency among the various photoresist processing steps, exposureis believed to be one of the most important steps in attaining highresolution photoresist images.

Reflection of activating radiation used to expose a photoresist oftenposes limits on resolution of the image patterned in the photoresistlayer. Reflection of radiation from the substrate/photoresist interfacecan produce spatial variations in the radiation intensity in thephotoresist, resulting in non-uniform photoresist linewidth upondevelopment. Radiation also can scatter from the substrate/photoresistinterface into regions of the photoresist where exposure isnon-intended, again resulting in linewidth variations.

One approach used to reduce the problem of reflected radiation has beenthe use of a radiation absorbing layer interposed between the substratesurface and the photoresist coating layer. See U.S. Pat. No. 7,425,403.

Electronic device manufacturers continually seek increased resolution ofa photoresist image patterned over antireflective coating layers.

In one aspect, we provide new resins that comprise (i) repeat units thatcomprise cyanurate-type groups; (ii) repeat units that comprisehydrophobic groups such as hydroxyl—polyol (e.g. diols), ethers, andcombinations thereof.

We found that underlying antireflective composition can be prone toundesired “lift-off” from a substrate surface during aqueous alkalinedevelopment of an overcoated photoresist layer. Such lift-off canseverely compromise resolution of the image patterned in that overcoatedresist layer.

We have now surprisingly found that incorporation of hydrophobic groupsin a cyanurate resin of an underlying antireflective composition cansubstantially enhance resolution of an overcoated photoresist layer,including a reduction in undesired lift-ff of the antireflective layer.

Such hydrophobic content may be imparted to a resin in a variety ofways. For example, hydrophobic groups may be grafted onto pre-formedresins. Compounds comprising one or more hydrophobic groups also may beco-polymerized with other compounds such as reactive monomers thatcomprise cyanurate functionality to form a resin of the invention.

In a preferred aspect, resins of the invention comprise cyanurate unitsthat comprise substitution of multiple cyanurate nitrogen ring atoms bydistinct (different) carboxy (e.g. —COOH) and/or carboxy ester (e.g.COOR where R is other than hydrogen such as C₁₋₁₂alkyl) substitution. Inthis aspect, particularly preferred resins of the invention may beprovided by reaction of compounds of the following Formula I:

wherein at least two of the radicals R¹OOC(CX₂)_(n)—, R²— andR³OOC(CX₂)_(m)— are different acid or ester groups; and

R¹, R², R³ and each X are each independently hydrogen or non-hydrogensubstituent such as optionally substituted alkyl (e.g. optionallysubstituted C₁₋₁₀ alkyl), optionally substituted alkenyl or alkynylpreferably having 2 to about 10 carbon atoms such as such as allyl,optionally substituted alkanoyl preferably having 1 to about 10 carbonatoms; optionally substituted alkoxy (including epoxy) preferably having1 to about 10 carbon atoms such as methoxy, propoxy, butoxy; optionallysubstituted alkylthio preferably having 1 to about 10 carbon atoms;optionally substituted alkylsulfinyl preferably 1 to about 10 carbonatoms; optionally substituted alkylsulfonyl preferably having 1 to about10 carbon atoms; optionally substituted carboxy preferably have 1 toabout 10 carbon atoms (which includes groups such as —COOR′ where R′ isH or C₁₋₈alkyl, including esters that are substantially non-reactivewith photoacid); optionally substituted alkaryl such as optionallysubstituted benzyl, optionally substituted carbocyclic aryl such asoptionally substituted phenyl, naphthyl, acenaphthyl, or optionallysubstituted heteralicyclic or heteroaromatic group such asmethylphthalimide, N-methyl-1,8-phthalimide;

n and m are the same or different and each a whole number e.g. 0, 1, 2,3 or 4, with n and/or m equal a positive integer such as 1 or 2 beingoften preferred.

For many embodiments, particularly preferred resins of the invention areprovided by reaction of compounds where one or more X groups arehydrogen such as compounds of the following Formula IA:

wherein at least two of the radicals R¹OOC(CH₂)_(n)—, R²— andR³OOC(CH₂)_(m)— are different acid or ester groups; and

wherein at least two of the radicals R¹OOC(CX₂)_(n)—, R²— andR³OOC(CX₂)_(m)— are different acid or ester groups; and

R¹, R² and R³ are each independently hydrogen or non-hydrogensubstituent such as optionally substituted alkyl (e.g. optionallysubstituted C₁₋₁₀ alkyl), optionally substituted alkenyl or alkynylpreferably having 2 to about 10 carbon atoms such as such as allyl,optionally substituted alkanoyl preferably having 1 to about 10 carbonatoms; optionally substituted alkoxy (including epoxy) preferably having1 to about 10 carbon atoms such as methoxy, propoxy, butoxy; optionallysubstituted alkylthio preferably having 1 to about 10 carbon atoms;optionally substituted alkylsulfinyl preferably 1 to about 10 carbonatoms; optionally substituted alkylsulfonyl preferably having 1 to about10 carbon atoms; optionally substituted carboxy preferably have 1 toabout 10 carbon atoms (which includes groups such as —COOR′ where R′ isH or C₁₋₈alkyl, including esters that are substantially non-reactivewith photoacid); optionally substituted alkaryl such as optionallysubstituted benzyl, optionally substituted carbocyclic aryl such asoptionally substituted phenyl, naphthyl, acenaphthyl, or optionallysubstituted heteralicyclic or heteroaromatic group such asmethylphthalimide, N-methyl-1,8-phthalimide;

n and m are the same or different and each a whole number e.g. 0, 1, 2,3 or 4, with n and/or m equal a positive integer such as 1 or 2 beingoften preferred.

By stating herein that at least two of the radicals R¹OOC(CX₂)_(n)—, R²—and R³OOC(CX₂)_(m)— are different acid or ester groups (or, in the caseof Formula IA, at least two of the radicals R¹OOC(CH₂)_(n)—, R²— andR³OOC(CH₂)_(m)— are different acid or ester groups), it is meant that atleast two radicals will have at least one atom difference. For example,if values of n and m are not equal, then the groups will be differentacid or ester groups. If the groups R¹ and R³ are not the same (e.g. R¹is —CH₃ and R³ is H), then the groups will be different acid or estergroups. If R² is an acid, and the R³ is other than hydrogen, then thegroups are different. In many cases, the radicals will differ by two ormore atoms.

In the above Formulae I and IA, preferred R¹ and R³ moieties includeoptionally substituted alkyl (which includes cycloalkyl), preferably analkyl (which includes cycloalkyl) having 3 to 8 carbons. R² groupscontaining acid moieties or alkyl ester moieties also are preferred.

In certain embodiments, preferred compounds are those of Formulae I andIA above wherein at least one of R¹, R² and R³ contain one or morehalogen atoms particularly one or more fluorine atoms and/or one or morechlorine atoms such as haloalkyl and alkylaryl (such as halophenyl orhalonaphthyl) e.g. —CF₃, >CF₂, —CHF₂, >CHF, —CH₂F, C₆H_(5-x)F_(x),C₆H_(5-x)Cl_(x), —CCl₃, ->CCl₂, —CHCl₂, ->CHCl, —CH₂Cl. Generallypreferred are compounds of Formulae I and IA where R² hashalogen-substitution.

In a yet further aspect, antireflective compositions are provided thatcomprises a resin as disclosed herein.

The group R² of the above Formulae I and IA can be useful to introducevarious functionalities to the subsequently polymers comprising thegroups, including to impart desired lithographic properties such asoptical properties, etch rates, thermal properties, solubility incoating solvents and coating properties over different substratesurfaces. The group R² of the above Formula I also can influence thepolymerization process for obtaining a more linear and higher molecularcoating polymer compositions.

As mentioned, preferred resins of the invention may be prepared usingone or more compounds of Formulae I and II as reagents. Particularlypreferred resins may include a tethered (covalently linked) crosslinkercomponent that provides hardening of an applied coating layer containingthe resin.

As discussed above, underlying coating compositions are also providedwhich preferably may include one or more resins as disclosed herein.Preferred additional components of an underlying composition include acrosslinking functionality or material. Preferred underlying coatingcompositions are formulated as organic solvent compositions for spin-onapplication to a desired substrate such as a microelectronic wafer.

Preferred coating compositions of the invention are crosslinked prior totreatment to modulate water contact angle. Such crosslinking includeshardening and covalent-bonding forming reactions between one or morecomposition components.

For antireflective applications, underlying compositions of theinvention also preferably contain a component that comprises chromophoregroups that can absorb undesired radiation used to expose the overcoatedresist layer from reflecting back into the resist layer. Suchchromophore groups may be present with other composition components suchas the resin(s) or an acid generator compound, or the composition maycomprise another component that may comprise such chromophore units,e.g. a small molecule (e.g. MW less than about 1000 or 500) thatcontains one or more chromophore moieties, such as one or moreoptionally substituted phenyl, optionally substituted anthracene oroptionally substituted naphthyl groups.

Generally preferred chromophores for inclusion in coating composition ofthe invention particularly those used for antireflective applicationsinclude both single ring and multiple ring aromatic groups such asoptionally substituted phenyl, optionally substituted naphthyl,optionally substituted anthracenyl, optionally substitutedphenanthracenyl, optionally substituted quinolinyl, and the like.Particularly preferred chromophores may vary with the radiation employedto expose an overcoated resist layer. More specifically, for exposure ofan overcoated resist at 248 nm, optionally substituted anthracene andoptionally substituted naphthyl are preferred chromophores of theantireflective composition. For exposure of an overcoated resist at 193nm, optionally substituted phenyl and optionally substituted naphthylare particularly preferred chromophores of the antireflectivecomposition. Preferably, such chromophore groups are linked (e.g.pendant groups) to a resin component of the antireflective composition.

As discussed above, coating compositions of the invention preferably arecrosslinking compositions and contain a material that will crosslink orotherwise cure upon e.g. thermal or activating radiation treatment.Typically, the composition will contain a crosslinker component, e.g. anamine-containing material such as a melamine, glycouril orbenzoguanamine compound or resin.

Preferably, crosslinking compositions of the invention can be curedthrough thermal treatment of the composition coating layer. Suitably,the coating composition also contains an acid or more preferably an acidgenerator compound, particularly a thermal acid generator compound, tofacilitate the crosslinking reaction.

For use as an antireflective coating composition, as well as otherapplications such as via-fill, preferably the composition is crosslinkedprior to applying a photoresist composition layer over the compositionlayer.

A variety of photoresists may be used in combination (i.e. overcoated)with a coating composition of the invention. Preferred photoresists foruse with the antireflective compositions of the invention arechemically-amplified resists, especially positive-acting photoresiststhat contain one or more photoacid generator compounds and a resincomponent that contains units that undergo a deblocking or cleavagereaction in the presence of photogenerated acid, such asphotoacid-labile ester, acetal, ketal or ether units. Negative-actingphotoresists also can be employed with coating compositions of theinvention, such as resists that crosslink (i.e. cure or harden) uponexposure to activating radiation. Preferred photoresists for use with acoating composition of the invention may be imaged with relativelyshort-wavelength radiation, e.g. radiation having a wavelength of lessthan 300 nm or less than 260 nm such as 248 nm, or radiation having awavelength of less than about 200 nm such as 193 nm.

The invention further provides methods for forming a photoresist reliefimage and novel articles of manufacture comprising substrates (such as amicroelectronic wafer substrate) coated with a coating composition ofthe invention alone or in combination with a photoresist composition.

Other aspects of the invention are disclosed infra.

We now provide new organic coating compositions that are particularlyuseful with an overcoated photoresist layer. Preferred coatingcompositions of the invention may be applied by spin-coating (spin-oncompositions) and formulated as a solvent composition. The coatingcompositions of the invention are especially useful as antireflectivecompositions for an overcoated photoresist and/or as planarizing orvia-fill compositions for an overcoated photoresist composition coatinglayer.

Resins:

As discussed above, resins of the invention comprise hydrophobic groupssuch as alcohol (including diol and other polyols), ether, and the like.

For example, a suitable monomer with hydrophobic groups can be reactedwith cyanurate monomers. Suitable hydrophobic reagents to forma resin ofthe invention include e.g. 2-propylene glycol, 1,2-butanediol,1,2-pentanediol,1,2-hexanediol, 1,2-decanediol, glycidyl isobutyl ether,glycidyl isopropyl ether, and glycidyl hexadecyl ether.

We have found that relatively low amounts of hydrophobic groups in aresin can provide effective results, i.e. enhanced resolution of anovercoated resist relief image. For instance, preferred resins suitablymay have from about 1 to 40 weight percent of total resin units comprisea hydrophobic moiety, more typically from 1 to 20 weight percent oftotal resin units comprising a hydrophobic moiety, or from 1 or 2 toabout 10 weight percent of total resin units comprising a hydrophobicmoiety.

The site of incorporation of a hydrophobic group (e.g. alcohol such asdiol) can be made at a higher relative proportion at the end polymerportion if the hydrophobic monomer has the polymerizable moiety (e.g.olefin) proximate (e.g. within 1, 2 or perhaps 3 carbon or other atomspacing) to the hydrophobic group (e.g. a 1,2-diol). The site ofincorporation of a hydrophobic group (e.g. alcohol such as diol) can bemade at a higher relative proportion within the polymer chain (ratherthan an end portion) if the hydrophobic monomer has the polymerizablemoiety (e.g. olefin) relatively distal (e.g. 2 or more, more typically3, 4, 5, 6, or 7 or more carbon or other atom spacing) to thehydrophobic group (e.g. diol).

Exemplary preferred resins of the invention may comprise the followingstructures:

As discussed above, preferred resins include those that are formed withone or more reagents selected from Formula I above. An acidic or basiccondensation reaction can be suitable. Preferably, the reagents selectedfrom Formula I constitute at least about 5 percent of the total repeatunits of the formed resin, more preferably at least about 10, 15, 20,25, 30, 35, 40, 45, 50 or 55 percent of the total repeat units of theformed resin.

One preferred synthesis route is depicted in the following Scheme I:

In the above Scheme I, R₂ and R₄ are the same as R² Formulae I and IAabove and may be readily grafted onto the monomer compounds e.g. asexemplified in the following Scheme II Each R₁ and R₃ in Scheme I aboveis independently the same as defined for R¹ and R³ in Formula I and IAabove:

In the above Scheme II, each R₁ is independently a group as defined forR¹ in Formula I above and preferably each R₁ of Scheme II isindependently e.g. hydrogen C₁₋₂₀alkyl preferably C₁₋₁₀alkyl,C₁₋₂₀alkoxy preferably C₁₋₁₀alkoxy, C₇₋₂₀alkylaryl, and R₂ in Scheme IIis the same as R² in Formula I above.

Suitable polyol reagents include diols, glycerols and triols such ase.g. diols such as diol is ethylene glycol, 1,2-propylene glycol,1,3-propylene glycol, butane diol, pentane diol, cyclobutyl diol,cyclopentyl diol, cyclohexyl diol, dimethylolcyclohexane, and triolssuch as glycerol, trimethylolethane, trimethylolpropane and the like.

Specifically suitable resin syntheses are also set forth in the exampleswhich follow.

As discussed, for antireflective applications, suitably one or more ofthe compounds reacted to form the resin comprise a moiety that canfunction as a chromophore to absorb radiation employed to expose anovercoated photoresist coating layer. For example, a phthalate compound(e.g. a phthalic acid or dialkyl phthalate (i.e. di-ester such as eachester having 1-6 carbon atoms, preferably a di-methyl or ethylphthalate) may be polymerized with an aromatic or non-aromatic polyoland optionally other reactive compounds to provide a polyesterparticularly useful in an antireflective composition employed with aphotoresist imaged at sub-200 nm wavelengths such as 193 nm. Similarly,resins to be used in compositions with an overcoated photoresist imagedat sub-300 nm wavelengths or sub-200 nm wavelengths such as 248 nm or193 nm, a naphthyl compound may be polymerized, such as a naphthylcompound containing one or two or more carboxyl substituents e.g.dialkyl particularly di-C₁₋₆alkyl naphthalenedicarboxylate. Reactiveanthracene compounds also are preferred, e.g. an anthracene compoundhaving one or more carboxy or ester groups, such as one or more methylester or ethyl ester groups.

The compound that contains a chromophore unit also may contain one orpreferably two or more hydroxy groups and be reacted with acarboxyl-containing compound. For example, a phenyl compound oranthracene compound having one, two or more hydroxyl groups may bereacted with a carboxyl-containing compound.

Additionally, underlying coating composition that are employed forantireflective purposes may contain a material that contains chromophoreunits that is separate from a resin component that provides watercontact angle modulation (e.g. a resin that contains photoacid-labilegroups and/or base-reactive groups. For instance, the coatingcomposition may comprise a polymeric or non-polymeric compound thatcontain phenyl, anthracene, naphthyl, etc. units. It is often preferred,however, that the one or more resins that provide water contact anglemodulation also chromophore moieties.

Preferably resins of underlying coating compositions of the inventionwill have a weight average molecular weight (Mw) of about 1,000 to about10,000,000 daltons, more typically about 2,000 to about 100,000 daltons,and a number average molecular weight (Mn) of about 500 to about1,000,000 daltons. Molecular weights (either Mw or Mn) of the polymersof the invention are suitably determined by gel permeationchromatography.

As mentioned, preferred underlying coating compositions of the inventioncan be crosslinked, e.g. by thermal and/or radiation treatment. Forexample, preferred underlying coating compositions of the invention maycontain a separate crosslinker component that can crosslink with one ormore other components of the coating composition. Generally preferredcrosslinking coating compositions comprise a separate crosslinkercomponent. Particularly preferred coating compositions of the inventioncontain as separate components: a resin, a crosslinker, and an acidsource such as a thermal acid generator compound. Thermal-inducedcrosslinking of the coating composition by activation of the thermalacid generator is generally preferred.

Suitable thermal acid generator compounds for use in a coatingcomposition include ionic or substantially neutral thermal acidgenerators, e.g. an ammonium arenesulfonate salt, for catalyzing orpromoting crosslinking during curing of an antireflective compositioncoating layer. Typically one or more thermal acid generators are presentin an coating composition in a concentration from about 0.1 to 10percent by weight of the total of the dry components of the composition(all components except solvent carrier), more preferably about 2 percentby weight of the total dry components.

Preferred crosslinking-type coating compositions of the invention alsocontain a crosslinker component. A variety of crosslinkers may beemployed, including those crosslinkers disclosed in Shipley EuropeanApplication 542008 incorporated herein by reference. For example,suitable coating composition crosslinkers include amine-basedcrosslinkers such as melamine materials, including melamine resins suchas manufactured by Cytec Industries and sold under the tradename ofCymel 300, 301, 303, 350, 370, 380, 1116 and 1130. Glycolurils areparticularly preferred including glycolurils available from CytecIndustries. Benzoquanamines and urea-based materials also will besuitable including resins such as the benzoquanamine resins availablefrom Cytec Industries under the name Cymel 1123 and 1125, and urearesins available from Cytec Industries under the names of Powderlink1174 and 1196. In addition to being commercially available, suchamine-based resins may be prepared e.g. by the reaction of acrylamide ormethacrylamide copolymers with formaldehyde in an alcohol-containingsolution, or alternatively by the copolymerization of N-alkoxymethylacrylamide or methacrylamide with other suitable monomers.

A crosslinker component of a coating composition of the invention ingeneral is present in an amount of between about 5 and 50 weight percentof total solids (all components except solvent carrier) of theantireflective composition, more typically in an amount of about 7 to 25weight percent total solids.

Coating compositions of the invention, particularly for reflectioncontrol applications, also may contain additional dye compounds thatabsorb radiation used to expose an overcoated photoresist layer. Otheroptional additives include surface leveling agents, for example, theleveling agent available under the tradename Silwet 7604, or thesurfactant FC 171 or FC 431 available from the 3M Company.

Underlying coating compositions of the invention also may contain othermaterials such as a photoacid generator, including a photoacid generatoras discussed for use with an overcoated photoresist composition. SeeU.S. Pat. No. 6,261,743 for a discussion of such use of a photoacidgenerator in an antireflective composition.

To make a liquid coating composition of the invention, the components ofthe coating composition are dissolved in a suitable solvent such as, forexample, one or more oxyisobutyric acid esters particularlymethyl-2-hydroxyisobutyrate as discussed above, ethyl lactate or one ormore of the glycol ethers such as 2-methoxyethyl ether (diglyme),ethylene glycol monomethyl ether, and propylene glycol monomethyl ether;solvents that have both ether and hydroxy moieties such as methoxybutanol, ethoxy butanol, methoxy propanol, and ethoxy propanol; methyl2-hydroxyisobutyrate; esters such as methyl cellosolve acetate, ethylcellosolve acetate, propylene glycol monomethyl ether acetate,dipropylene glycol monomethyl ether acetate and other solvents such asdibasic esters, propylene carbonate and gamma-butyro lactone. Theconcentration of the dry components in the solvent will depend onseveral factors such as the method of application. In general, thesolids content of an underlying coating composition varies from about0.5 to 20 weight percent of the total weight of the coating composition,preferably the solids content varies from about 0.5 to 10 weight of thecoating composition.

Exemplary Photoresist Systems

A variety of photoresist compositions can be employed with coatingcompositions of the invention, including positive-acting andnegative-acting photoacid-generating compositions. Photoresists usedwith antireflective compositions of the invention typically comprise aresin binder and a photoactive component, typically a photoacidgenerator compound. Preferably the photoresist resin binder hasfunctional groups that impart alkaline aqueous developability to theimaged resist composition.

As discussed above, particularly preferred photoresists for use withunderlying coating compositions of the invention arechemically-amplified resists, particularly positive-actingchemically-amplified resist compositions, where the photoactivated acidin the resist layer induces a deprotection-type reaction of one or morecomposition components to thereby provide solubility differentialsbetween exposed and unexposed regions of the resist coating layer. Anumber of chemically-amplified resist compositions have been described,e.g., in U.S. Pat. Nos. 4,968,581; 4,883,740; 4,810,613; 4,491,628 and5,492,793. Coating compositions of the invention are particularlysuitably used with positive chemically-amplified photoresists that haveacetal groups that undergo deblocking in the presence of a photoacid.Such acetal-based resists have been described in e.g. U.S. Pat. Nos.5,929,176 and 6,090,526.

Underlying coating compositions of the invention also may be used withother positive resists, including those that contain resin binders thatcomprise polar functional groups such as hydroxyl or carboxylate and theresin binder is used in a resist composition in an amount sufficient torender the resist developable with an aqueous alkaline solution.Generally preferred resist resin binders are phenolic resins includingphenol aldehyde condensates known in the art as novolak resins, homo andcopolymers or alkenyl phenols and homo and copolymers ofN-hydroxyphenyl-maleimides.

Preferred positive-acting photoresists for use with an underlyingcoating composition of the invention contains an imaging-effectiveamount of photoacid generator compounds and one or more resins that areselected from the group of:

1) a phenolic resin that contains acid-labile groups that can provide achemically amplified positive resist particularly suitable for imagingat 248 nm. Particularly preferred resins of this class include: i)polymers that contain polymerized units of a vinyl phenol and an alkylacrylate, where the polymerized alkyl acrylate units can undergo adeblocking reaction in the presence of photoacid. Exemplary alkylacrylates that can undergo a photoacid-induced deblocking reactioninclude e.g. t-butyl acrylate, t-butyl methacrylate, methyladamantylacrylate, methyl adamantyl methacrylate, and other non-cyclic alkyl andalicyclic acrylates that can undergo a photoacid-induced reaction, suchas polymers in U.S. Pat. Nos. 6,042,997 and 5,492,793; ii) polymers thatcontain polymerized units of a vinyl phenol, an optionally substitutedvinyl phenyl (e.g. styrene) that does not contain a hydroxy or carboxyring substituent, and an alkyl acrylate such as those deblocking groupsdescribed with polymers i) above, such as polymers described in U.S.Pat. No. 6,042,997; and iii) polymers that contain repeat units thatcomprise an acetal or ketal moiety that will react with photoacid, andoptionally aromatic repeat units such as phenyl or phenolic groups; suchpolymers have been described in U.S. Pat. Nos. 5,929,176 and 6,090,526.

2) a resin that is substantially or completely free of phenyl or otheraromatic groups that can provide a chemically amplified positive resistparticularly suitable for imaging at sub-200 nm wavelengths such as 193nm. Particularly preferred resins of this class include: i) polymersthat contain polymerized units of a non-aromatic cyclic olefin(endocyclic double bond) such as an optionally substituted norbornene,such as polymers described in U.S. Pat. Nos. 5,843,624, and 6,048,664;ii) polymers that contain alkyl acrylate units such as e.g. t-butylacrylate, t-butyl methacrylate, methyladamantyl acrylate, methyladamantyl methacrylate, and other non-cyclic alkyl and alicyclicacrylates; such polymers have been described in U.S. Pat. No. 6,057,083;European Published Applications EP01008913A1 and EP00930542A1; and U.S.pending patent application Ser. No. 09/143,462; iii) polymers thatcontain polymerized anhydride units, particularly polymerized maleicanhydride and/or itaconic anhydride units, such as disclosed in EuropeanPublished Application EP01008913A1 and U.S. Pat. No. 6,048,662.

3) a resin that contains repeat units that contain a hetero atom,particularly oxygen and/or sulfur (but other than an anhydride, i.e. theunit does not contain a keto ring atom), and preferable aresubstantially or completely free of any aromatic units. Preferably, theheteroalicyclic unit is fused to the resin backbone, and furtherpreferred is where the resin comprises a fused carbon alicyclic unitsuch as provided by polymerization of a norborene group and/or ananhydride unit such as provided by polymerization of a maleic anhydrideor itaconic anhydride. Such resins are disclosed in PCT/US01/14914 andU.S. application Ser. No. 09/567,634.

4) a resin that contains fluorine substitution (fluoropolymer), e.g. asmay be provided by polymerization of tetrafluoroethylene, a fluorinatedaromatic group such as fluoro-styrene compound, and the like. Examplesof such resins are disclosed e.g. in PCT/US99/21912.

Suitable photoacid generators to employ in a positive or negative actingphotoresist overcoated over a coating composition of the inventioninclude imidosulfonates such as compounds of the following formula:

wherein R is camphor, adamantane, alkyl (e.g. C₁₋₁₂ alkyl) andfluoroalkyl such as fluoro (C₁₋₁₈alkyl) e.g. RCF₂— where R is optionallysubstituted adamantyl.

Also preferred is a biphenyl sulfonium PAG, complexed with anions suchas the sulfonate anions mentioned above, particularly a perfluoroalkylsulfonate such as perfluorobutane sulfonate.

Other known PAGS also may be employed in the resists of the invention.Particularly for 193 nm imaging, generally preferred are PAGS that donot contain aromatic groups, such as the above-mentionedimidosulfonates, in order to provide enhanced transparency.

Other suitable photoacid generators for use in compositions of theinvention include for example: onium salts, for example,triphenylsulfonium trifluoromethanesulfonate,(p-tert-butoxyphenyl)diphenylsulfonium trifluoromethanesulfonate,tris(p-tert-butoxyphenyl)sulfonium trifluoromethanesulfonate,triphenylsulfonium p-toluenesulfonate, nitrobenzyl derivatives, forexample, 2-nitrobenzyl p-toluenesulfonate, 2,6-dinitrobenzylp-toluenesulfonate, and 2,4-dinitrobenzyl p-toluenesulfonate; sulfonicacid esters, for example, 1,2,3-tris(methanesulfonyloxy)benzene,1,2,3-tris(trifluoromethanesulfonyloxy)benzene, and1,2,3-tris(p-toluenesulfonyloxy)benzene; diazomethane derivatives, forexample, bis(benzenesulfonyl)diazomethane,bis(p-toluenesulfonyl)diazomethane; glyoxime derivatives, for example,bis-O-(p-toluenensulfonyl)-α-dimethylglyoxime, andbis-O-(n-butanesulfonyl)-α-dimethylglyoxime; sulfonic acid esterderivatives of an N-hydroxyimide compound, for example,N-hydroxysuccinimide methanesulfonic acid ester, N-hydroxysuccinimidetrifluoromethanesulfonic acid ester; and halogen-containing triazinecompounds, for example,2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-1,3,5-triazine, and2-(4-methoxynaphthyl)-4,6-bis(trichloromethyl)-1,3,5-triazine. One ormore of such PAGs can be used.

A preferred optional additive of resists of the invention is an addedbase, particularly tetrabutylammonium hydroxide (TBAH), ortetrabutylammonium lactate, which can enhance resolution of a developedresist relief image. For resists imaged at 193 nm, a preferred addedbase is a lactate salt of tetrabutylammonium hydroxide as well asvarious other amines such as triisopropanol, diazabicyclo undecene ordiazabicyclononene. The added base is suitably used in relatively smallamounts, e.g. about 0.03 to 5 percent by weight relative to the totalsolids.

Preferred negative-acting resist compositions for use with an overcoatedcoating composition of the invention comprise a mixture of materialsthat will cure, crosslink or harden upon exposure to acid, and aphotoacid generator.

Particularly preferred negative-acting resist compositions comprise aresin binder such as a phenolic resin, a crosslinker component and aphotoactive component of the invention. Such compositions and the usethereof have been disclosed in European Patent Applications 0164248 and0232972 and in U.S. Pat. No. 5,128,232 to Thackeray et al. Preferredphenolic resins for use as the resin binder component include novolaksand poly(vinylphenol)s such as those discussed above. Preferredcrosslinkers include amine-based materials, including melamine,glycolurils, benzoguanamine-based materials and urea-based materials.Melamine-formaldehyde resins are generally most preferred. Suchcrosslinkers are commercially available, e.g. the melamine resins soldby Cytec Industries under the trade names Cymel 300, 301 and 303.Glycoluril resins are sold by Cytec Industries under trade names Cymel1170, 1171, 1172, Powderlink 1174, and benzoguanamine resins are soldunder the trade names of Cymel 1123 and 1125.

Photoresists of the invention also may contain other optional materials.For example, other optional additives include anti-striation agents,plasticizers, speed enhancers, dissolution inhibitors, etc. Suchoptional additives typically will be present in minor concentrations ina photoresist composition except for fillers and dyes which may bepresent in relatively large concentrations, e.g., in amounts of fromabout 5 to 30 percent by weight of the total weight of a resist's drycomponents.

Lithographic Processing

In use, a coating composition of the invention is applied as a coatinglayer to a substrate by any of a variety of methods such as spincoating. The coating composition in general is applied on a substratewith a dried layer thickness of between about 0.02 and 0.5 μm,preferably a dried layer thickness of between about 0.04 and 0.20 μm.The substrate is suitably any substrate used in processes involvingphotoresists. For example, the substrate can be silicon, silicon dioxideor aluminum-aluminum oxide microelectronic wafers. Gallium arsenide,silicon carbide, ceramic, quartz or copper substrates may also beemployed. Substrates for liquid crystal display or other flat paneldisplay applications are also suitably employed, for example glasssubstrates, indium tin oxide coated substrates and the like. Substratesfor optical and optical-electronic devices (e.g. waveguides) also can beemployed.

Preferably the applied coating layer is cured before a photoresistcomposition is applied over the underlying coating composition. Cureconditions will vary with the components of the underlying coatingcomposition. Particularly the cure temperature will depend on thespecific acid or acid (thermal) generator that is employed in thecoating composition. Typical cure conditions are from about 80° C. to225° C. for about 0.5 to 5 minutes. Cure conditions preferably renderthe coating composition coating layer substantially insoluble to thephotoresist solvent as well as an alkaline aqueous developer solution.

After such curing, a photoresist is applied above the surface of theapplied coating composition. As with application of the bottom coatingcomposition layer(s), the overcoated photoresist can be applied by anystandard means such as by spinning, dipping, meniscus or roller coating.Following application, the photoresist coating layer is typically driedby heating to remove solvent preferably until the resist layer is tackfree. Optimally, essentially no intermixing of the bottom compositionlayer and overcoated photoresist layer should occur.

The resist layer is then imaged with activating radiation through a maskin a conventional manner. The exposure energy is sufficient toeffectively activate the photoactive component of the resist system toproduce a patterned image in the resist coating layer. Typically, theexposure energy ranges from about 3 to 300 mJ/cm² and depending in partupon the exposure tool and the particular resist and resist processingthat is employed. The exposed resist layer may be subjected to apost-exposure bake if desired to create or enhance solubilitydifferences between exposed and unexposed regions of a coating layer.For example, negative acid-hardening photoresists typically requirepost-exposure heating to induce the acid-promoted crosslinking reaction,and many chemically amplified positive-acting resists requirepost-exposure heating to induce an acid-promoted deprotection reaction.Typically post-exposure bake conditions include temperatures of about50° C. or greater, more specifically a temperature in the range of fromabout 50° C. to about 160° C.

The photoresist layer also may be exposed in an immersion lithographysystem, i.e. where the space between the exposure tool (particularly theprojection lens) and the photoresist coated substrate is occupied by animmersion fluid, such as water or water mixed with one or more additivessuch as cesium sulfate which can provide a fluid of enhanced refractiveindex. Preferably the immersion fluid (e.g., water) has been treated toavoid bubbles, e.g. water can be degassed to avoid nanobubbles.

References herein to “immersion exposing” or other similar termindicates that exposure is conducted with such a fluid layer (e.g. wateror water with additives) interposed between an exposure tool and thecoated photoresist composition layer.

The exposed resist coating layer is then developed, preferably with anaqueous based developer such as an alkali exemplified by tetra butylammonium hydroxide, sodium hydroxide, potassium hydroxide, sodiumcarbonate, sodium bicarbonate, sodium silicate, sodium metasilicate,aqueous ammonia or the like. Alternatively, organic developers can beused. In general, development is in accordance with art recognizedprocedures. Following development, a final bake of an acid-hardeningphotoresist is often employed at temperatures of from about 100° C. toabout 150° C. for several minutes to further cure the developed exposedcoating layer areas.

The developed substrate may then be selectively processed on thosesubstrate areas bared of photoresist, for example, chemically etching orplating substrate areas bared of photoresist in accordance withprocedures well known in the art. Suitable etchants include ahydrofluoric acid etching solution and a plasma gas etch such as anoxygen plasma etch. A plasma gas etch removes the underlying coatinglayer.

A plasma etch conducted by the following protocol: a coated substrate(e.g., substrate coated with an underlying coating composition andresist in accordance with the invention) is placed in a plasma etchchamber (e.g., Mark II Oxide Etch Chamber) at 25 mT pressure, top powerof 600 watts, 33 CHF₃ (Sccm), 7 O₂ (Sccm) and 80 Ar (Sccm).

The following non-limiting examples are illustrative of the invention.All documents mentioned herein are incorporated herein by reference.

EXAMPLE 1 General Synthesis Procedure to Prepare Monomers of Formula IAccording to Scheme II Above

Butyl bis(CarboxyEthyl)IsoCyanuric acid) esters, 200 g, is dissolved in525 g THF at room temperature. The homogenous solution is cooled to 0°C. in an ice bath followed by the addition of 125.14 g benzyl bromide.When a clear solution is obtained, 98.7 g of1,8-diazabicyclo[5.4.0]-undec-7-ene, DBU, is slowly added to thereaction mixture. On complete addition of DBU, the contents are stirredovernight at room temperature to obtain thick white precipitate of thesalt. The precipitates are filtered and the organic phase diluted byaddition of 500 ml ethyl acetate. The combined organic phase is washedwith 0.1N HCl followed by water washes to obtain a neutral pH on theaqueous phase. The organic phase is dried with sodium sulfate followedby vacuum drying to yield about 210 g of a viscous oil. The purity ofthe monomer was determined using ¹H NMR, ¹³C NMR and HPLC to be about>99%.

Example 2 to 12 are other useful monomers prepared according to thegeneral procedure of Example 1.

In the following Table, the group R₁ designates the R₁ substituent of acompound C as set forth in Scheme II above, and R₂ designates the R₂substituent of a compound A as set forth in Scheme II above.

TABLE 1 Example R₁ R₂ 2 —CH₂CH₃ —CH₃ 3 —CH₂CH₃ —CH₂I 4 —CH₂CH₃—CH₂CHOHCH₃ 5 —CH₂CH₂CH₂CH₃ —CH₂CH═CH₂ 6 —CH₂CH₂CH₂CH₃

7 —CH₂CH₂CH₂CH₃

8 —CH₂CH₂CH₂CH₃ —CH₂COOC(CH3)₃ 9 —CH₂CH₂CH₂CH₃

10 —CH₂CH₂CH₂CH₃

11 —CH₂CH₂CH₂CH₃

12 —CH₂CH₂CH₂CH₃

EXAMPLE 13 Alkylation of Butyl Bis(CarboxyEthyl)IsoCyanuric Acid) Esterswith Epichlorohydrin

Butyl bis(CarboxyEthyl)IsoCyanuric acid) esters, 30 g, Sodium Carbonate,8.16 g, Benzyl Trimethyl Ammonium Chloride (3.85 mmol), Epichlorohydrin,8.5 g, and 100 mL of Dioxane were charged into a 250 mL round bottomflask equipped with a magnetic stirrer and overhead condenser. The flaskwas placed in an oil bath set at 90° C. and allowed to stir for 12hours. The reaction contents were allowed to cool and diluted with 200mL of distilled water. The contents were then extracted into Ethylacetate (300 mL) and washed twice with 200 mL portions of water, driedover sodium sulfate and followed by solvent removed on a rotaryevaporator. The product was further dried under vacuum to afford aviscous oil (30 g, 89% yields).

EXAMPLE 14

To a 500 ml, 3 neck round bottom flask was charged with 100 g of monomerB (R₃ is H), 133.18 g of monomer of Example 5, 2.25 g ofpara-toluenesulfonic acid, and 164 g of anisole. The flask was heated to140°-160° C. while the contents were vigorously stirred. Butanol alongwith anisole was slowly distilled out of the reaction flask. 145 g ofdistillate was collected over a 6 hr time period. The viscous polymersolution was then diluted with 509 g of methyl-2-hydroxy isobutyrate. A100 g sample of this solution was added to 1000 mL isopropanol toprecipitate to polymer. The resulting precipitate was collected on afilter, partially air dried followed by vacuum oven drying to yield awhite powders whose characteristics are presented in Table 2.

The procedure according to Example 14 was used to prepare polymers ofExamples 15 to 22. Monomer B has the structure of compound B in Scheme Iabove with R₃═H, R₄═(CH₂)₂OH; references throughout these examples toMonomer B indicates the structure of compound B in Scheme I above suchR₃ and R₄ groups, this Monomer B also known as THEIC. Thecharacteristics of the polymers, as well as those of Example 14 arepresented in Table 2. In Table 2, references to Monomer A refer to astructure A as depicted in Scheme II above.

TABLE 2 Monomer Polymer A of Monomer Example Example A/B ratio Mw PDn₁₉₃ k₁₉₃ 14 5 45/55 8160 1.88 1.997 0.32 15 2 50/60 2200 ::::: 1.9870.315 16 6 50/50 2130 1.88 1.988 0.512 17 7 50/50 2650 1.48 1.965 0.32318 8 50/50 6800 2.71 1.947 0.26 19 9 50/50 20780 3.77 1.927 0.244 20 1150/50 28000 ::::: 2.015 0.398 21 12 50/50 3920 1.48 1.965 0.323 22 450/50 5000 1.95 1.957 0.303

EXAMPLE 23

Using the procedure according to Example 14 a ter-polymers was preparedcomprising of monomer A of Example 8, monomer B (R₃═H) at a feed ratioof 1:1 in excess 1,2-propanediol. Thus the condensation produced apolymer with Mw of 7460, PD of 2.5, n₁₉₃ of 1.926 and k₁₉₃ of 0.24.

EXAMPLE 24 Anti-Reflective Polymer Comprising of Tri-Acid andTri-Alcohol

To a 1000 ml, 3 neck round bottom flask was charged with 304 g oftris(2-hydroxyethyl)isocyanurate, 201.0 g oftris(2-carboxyethyl)isocyanurae, 5.39 g of para-toluene sulfonic acidmono-hydrae, 201.1 g of n-butanol, and 342 g of anisole. The flask washeated to 140°-160° C. and the contents were vigorously stirred. Butanolalong with anisole was slowly distilled out of the reaction flask.Polymers were varying Mw were synthesized by controlling the amount ofthe distillate. The polymer solution was then diluted with 1587 g ofmethyl 2-hydroxyisobutyrate. The resulting solution was neutralized withtriethyl amine and the product precipitation into a 10 fold volumesolution of isopropyl alcohol/methyl t-butyl ether (50/50). The polymerwas collected and dried under vacuum at 40° C.-60° C. overnight. TheGPC_((THF)) Mw was 4623 with a polydispersity of 1.68 and with n₁₉₃ of1.926 and k₁₉₃ of 0.24

In order to reduce sublimation, a crosslinker such as tetra methoxymethyl glycouril is covalently attached to the anti-reflective polymer.

EXAMPLE 25

About 700 g of polymer solution from Example 14 was heated at 50° C.followed by the addition of 140 g methyl-2-hydroxyisobutyrate, and 35 gof tetramethoxymethyl glycoluril, The contents were stirred for 3 hoursat 50° C. The reaction contents were then cooled to ambient temperatureand neutralized with triethyl amine. Precipitation was carried out of60/40 isopropanol/heptane (10 fold excess). The precipitates were washedwith heptane and vacuum dried overnight to provide a polymer of theabove structure. The resulting polymer Mw was 22175, PD of 6.18, n₁₉₃ of1.993 and k₁₉₃ of 0.32. Using C¹³ NMR was estimated that about 13.5weight percent cross-linker was attached to the polymer.

Examples 26 and 27 are representative of anti-reflecting coatingcompositions of the invention.

EXAMPLE 26

An anti-reflective casting solution comprising of 3.237 g of polymerfrom Example 19, 5.768 g of tetramethoxymethyl glycoluril, 0.371 gsolution of ammoniated para-toluene sulfonic acid and 490.624 g ofmethyl-2-hydroxyisobutyrate was filtered through a 0.2μ Teflon filterand spin cast at over silicon wafer. The film was baked at 205° C. for60 seconds, the thickness measured and than covered with a puddle ofPGMEA for 60 seconds. After spun dry the film thickness was measuredagain. No significant thickness loss or gain was detected. The lack offilm thickness loss or gain was also observed when a new film, processedin the same manner, was covered with MF26A developer for 60 seconds.These tests indicate that the cured films are highly cross-linked andunaffected by the solvent or developer.

EXAMPLE 27

It can be desirable to blend anti-reflective polymer compositions of theinvention to optimize coating and optical properties demanded by theapplication. Thus a solution comprising of 1.913 g of polymer of Example19, 1.913 g of polymer of Example 25, 4.29 g of tetramethoxymethylglycoluril, 0.371 g solution of ammoniated para-toluene sulfonic acidand 490.624 g of methyl-2-hydroxyisobutyrate was filtered through a 0.2μTeflon filter and spin cast at over silicon wafer. Following the bakeand strip test procedures used in Example 26 the films were foundunaffected by PGMEA (propylene glycol methyl ether acetate) and the 0.26N aqueous alkaline developer.

EXAMPLE 28 Synthesis and Characteristics of Polymer II

500 ml, 3 neck round bottom flask was charged with THEIC, 70 g (0.268mol), Butyl-BCEIC-tBu acetate, 133.86 g (0.0.268 mol), cyclohexylmethanol, 30.60 g (0.268 mol), p-TSA 1.99 g (1 wt % of total monomers),and anisole, 142.7 g. The flask was heated to 140°-160° C. and thecontents were vigorously stirred. n-Butanol along with anisole wasslowly distilled out of the reaction flask. Polymer Mw range ismaintained by controlling the amount of the distillate. The polymerreaction solution was then diluted with methyl-2-hydroxy isobutyrate,650 g. The resulting solution was heated to 50° C. followed by theaddition of 45.5 g tetra methoxy methyl glycouril and an additional 187g of methyl-2-hydroxy isobutyrate. The contents were gently stirred for3 hrs at this temperature. After three hours the reaction mixture wasneutralized with triethyl amine and the polymer precipitated into 10volumes of isopropyl alcohol/Methyl t-butyl ether (50/50). The polymerwas dried in vacuum oven at 40° C.-60° C. and then characterized by GPC,C¹³ NMR and ollepsometry (WVASE32 ollipsometer). The polymer showed Mwof about 16,000 Daltons, about 23% pendant glycoluril group, and n₁₉₃ of1.93 and k₁₉₃ of 0.27. The polymer self cross-linking characteristic wastested following the procedure outlined in Example 26. No significantfilm thickness loss was observed when the cured polymer film was coveredwith PGMEA and 0.26N developer.

EXAMPLE 29 Synthesis of C-Glycerol-Decanediol Polymer

Monomer C (Compound C of Scheme II above where R₁ is H) (200 g, 45 mol%), glycerol (60 g, 40 mol %) and 1,2-decanediol (42.5 g, 15 mol %) arecharged in a 1000 ml 3 neck round bottom flask followed by the additionof 1 weight % p-TSA and anisole. The contents are shaken vigorously at145° C. for 5-7 hrs to collect about 35 g-45 g distillate. The reactionis quenched by lowering down the reaction temperature to 80° C. andfollowed by the addition of THF. Residual monomer C is filtered and thefiltrate was precipitated out of methyl-t-butyl ether/isopropanol (50/50v/v) mix to yield a white powder which was dried in the vacuum ovenunder heat. The polymer could be precipitated from a variety of othersolvents like heptane, di-isopropyl ether etc.

The polymer was subjected to various analytical tests.

¹³C NMR reveals a composition consisting of 54% monomer C(R₁ is H), 43%glycerol and 3% 1,2-decanediol. Optical properties: n₁₉₃: 1.949; k₁₉₃:0.192

Other polymers with varying composition can be synthesized by increasingor decreasing the charge amounts of the diol monomer. Polymercomposition can also be varied to an extent by fractionation indifferent precipitation solvent mixtures.

For example the above polymer was enriched in diol content whenprecipitated from a solvent mixture of different polarity to give a newpolymer composition comprising of 48% monomer C (Compound C of Scheme IIabove where R₁ is H), 47% glycerol and 5.5% decanediol as determined by¹³C NMR.

EXAMPLE 30 Incorporation of Hydrophobic Component within the PolymerChain

Without being bound by any theory, it is believed that because of stericfactors the incorporation of a large hydrophobic monomer such as1,2-decanediol occurs primarily at the end of the polymer chain. Forimproved distribution of the hydrophobic component within the polymerchain it is desirable to use a monomer where the hydrophobic componentis further away from the reactive polymerizing groups.

Condensation of monomer C₁ (Compound C of Scheme II above where R₁ isButyl, R₂ is cyclohexylethyl) with monomer C(R₁ and R₂ are H) andglycerol Monomer C₁ is prepared according to Scheme II above.

The hydrophobic component can be incorporated in the polymer by usingMonomer C₁ (R₁ is Butyl, R₂ is cyclohexylethyl), Monomer C (R₁ and R₂ isH) and glycerol or other polyols.

Polymer synthesis is carried out according to Example 14 above.

As exemplary polymer structure is as follows.

What is claimed is:
 1. A coating composition for use with an overcoatedphotoresist, the coating composition comprising a resin comprisingcyanurate groups and hydrophobic groups, wherein the resin has halogensubstitution.
 2. The coating composition of claim 1 wherein thehydrophobic groups are selected from hydroxy and ether.
 3. The coatingcomposition of claim 1 wherein the resin is prepared from reagentscomprising a cyanurate compound comprising substitution of multiplecyanurate nitrogen ring atoms by distinct carboxy and/or carboxy estergroups.
 4. The coating composition of claim 3 wherein the cyanuratecompound corresponds to the following Formula I:

wherein at least two of the radicals R¹OOC(CX₂)_(n)—, R²— andR³OOC(CX₂)_(n)— are different acid or ester groups; and R¹, R² and R³and each X are each independently hydrogen or non-hydrogen substituents;and n and m are the same or different and each a whole number.
 5. Acoating composition of claim 1 wherein the resin comprises a covalentlylinked crosslinker group.
 6. A coating composition of claim 1 whereinthe resin comprises polyester linkages.
 7. A coated substratecomprising: a layer of an antireflective composition of claim 1; aphotoresist layer over the coating composition layer.
 8. A method offorming a photoresist relief image, comprising: applying anantireflective coating composition on a substrate, the antireflectivecoating composition comprising a resin comprising cyanurate groups andhydrophobic groups, wherein the resin has halogen substitution; applyinga photoresist composition above the coating composition layer; andexposing and developing the photoresist layer to provide a resist reliefimage.
 9. The method of claim 8 wherein the antireflective compositionis crosslinked prior to applying the photoresist composition.
 10. Thecoating composition of claim 3 wherein the cyanurate compoundcorresponds to the following Formula IA:

wherein at least two of the radicals R¹OOC(CH₂)_(n)—, R²— andR³OOC(CH₂)_(m)— are different acid or ester groups; R¹, R² and R³ areeach independently hydrogen or non-hydrogen substituent; and n and m arethe same or different and each a positive integer.
 11. The coatingcomposition of claim 10 wherein in Formula IA: R¹, R² and R³ are eachoptionally substituted C₁₋₁₀ alkyl, optionally substituted alkenyl oralkynyl having 2 to 10 carbon atoms, optionally substituted alkanoylhaving 1 to 10 carbon atoms; optionally substituted alkoxy having 1 to10 carbon atoms; optionally substituted alkylthio having 1 to 10 carbonatoms; optionally substituted alkylsulfinyl 1 to 10 carbon atoms;optionally substituted alkylsulfonyl having 1 to 10 carbon atoms;optionally substituted carboxy have 1 to 10 carbon atoms; optionallysubstituted alkaryl, optionally substituted carbocyclic aryl; oroptionally substituted heteralicyclic or heteroaromatic group; and n andm are each a positive integer.
 12. The coating composition of claim 1wherein the resin has fluorine substitution.
 13. The method of claim 8wherein the resin has fluorine substitution.
 14. The method of claim 8wherein the resin is prepared from reagents comprising a compoundcorresponding to the following Formula I:

wherein at least two of the radicals R¹OOC(CX₂)_(n)—, R²— andR³OOC(CX₂)_(n)— are different acid or ester groups; and R¹, R² and R³and each X are each independently hydrogen or non-hydrogen substituents;and n and m are the same or different and each a whole number.
 15. Themethod of claim 8 wherein the resin is prepared from reagents comprisinga compound corresponding to the following Formula IA:

wherein at least two of the radicals R¹OOC(CH₂)_(n)—, R²— andR³OOC(CH₂)_(m)— are different acid or ester groups; R¹, R² and R³ areeach independently hydrogen or non-hydrogen substituent; and n and m arethe same or different and each a positive integer.
 16. The method ofclaim 15 wherein in Formula IA: R¹, R² and R³ are each optionallysubstituted C₁₋₁₀ alkyl, optionally substituted alkenyl or alkynylhaving 2 to 10 carbon atoms, optionally substituted alkanoyl having 1 to10 carbon atoms; optionally substituted alkoxy having 1 to 10 carbonatoms; optionally substituted alkylthio having 1 to 10 carbon atoms;optionally substituted alkylsulfinyl 1 to 10 carbon atoms; optionallysubstituted alkylsulfonyl having 1 to 10 carbon atoms; optionallysubstituted carboxy have 1 to 10 carbon atoms; optionally substitutedalkaryl, optionally substituted carbocyclic aryl; or optionallysubstituted heteralicyclic or heteroaromatic group; and n and m are eacha positive integer.
 17. The method of claim 8 wherein the resincomprises polyester linkages.